Molecularly engineered superlattice hybrids consisting of periodic and alternating cores of porphyrin molecules separated by nanoscale silica walls were synthesized through a one-step organic inorganic hierarchical self-assembly approach. The self-assembly process not only could lock both porphyrin and inorganic building blocks into ordered 3D nanostructure but also could allow for the molecular-level controllable organization of porphyrin molecules in the central regions of the silica pore channels, which leads to the formation of porphyrin core-silica wall superlattice hybrids with molecular-scale and mesoscale ordering. It was demonstrated that both the mesostructure and morphology of the hybrids can be finely tailored by turning the cooperative self-assembly process. It is significant that the hybrids show self-assembled optical properties consistent with the orientational arrangement of the porphyrins within periodic nanoscale silica channels. The methodology introduced herein demonstrates high versatility with respect to the self-assembly of optical active macrocycles into highly ordered superlattice hybrid architectures.